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United States Patent 3,342,542 DYEING AND PRINTING 0F POLYESTER ANDTRIACETATE FIBERS WITH A GLYCEROL DI ARYLETHER CARRIER Max Morf, Riehen,and Gerhard Koegel, Reinach, Basel- Land, Switzerland, assignors to CibaLimited, Basel, Switzerland, a company of Switzerland No Drawing. FiledNov. 22, 1965, Ser. No. 509,202 Claims priority, applicationSwitzerland, Nov. 25, 1964,

6 Claims. (Cl. 8-55) The present invention provides a process forcoloring, i.e. dyeing or printing textile materials from polyesterand/or triacetate fibers with dyestuffs that are sparingly soluble toinsoluble in water and in the presence of a carrier, wherein at leastone compound of the formula --where R and R are identical ordilferentaryl radicalsis added as carrierto the coloring preparation.

The textile materials to be dyed by the present process consist ofpolyester fibers and/or triacetate fibers. Polyester fibers areprimarily fibers from high-melting linear polyethylenegylcolterephthalate. The term 'triacetate describes products such as areobtained above all by acetylating cellulose with acetic anhydride andsulfuric acid in methylenechloride as solvent in spinning.

Both types of fibers, or mixtures of these two types of fibers, are dyedor printed with developing dyestuffs or their components or with vatdyes or in the first place with disperse dyestuffs. The term dispersedyestuffs describes organic colored compounds of which at most onlytraces are water-soluble and which must therefore be applied in the formof aqueous dispersions; they may belong to a wide variety of types ofdyestuffs and belong preferably to the azo and aminoanthaquinonedyestuffs.

To ensure that the aforementioned aqueous dispersion yield satisfactoryresults on the hydrophobic synthetic fibrous material even underunfavourable conditions, socalled carriers are incorporated with thedyeing preparations to be used. A carrier is an aliphatic, aromatic oraliphatic-aromatic compound which is soluble or insoluble in water andis capable of swelling when acted upon by the fibrous material, wherebythe penetration of the dyestutf into the fibre is facilitated.

It has now been found that diethers of sponding to the formula where Rand R represent identical or different aryl radicals-are particularlysuitable carriers.

From among the compounds oQtaz/Formula (1) those are especially suitablewhich correspond to the formula (2) A1 glycerol corre- Of special valueare those compounds in which the alkyl .radicals contain 1 to 8 carbonatoms and at least one alkyl. radical is in ortho-position, relativelyto the ether bridge. A compound ofthis definition corresponds to theformula I OH alkyl where A, B and B have the above meanings and thealkyl radical contains 1 to 8 carbon atoms. However, owing to theirready accessibility the symmetrical compounds occupy a favoured positionand from among these there may be specially mentioned those compoundswhich are substituted exclusively by alkyl radicals. It may also beemphasized that the number of substituents that may be present in eachbenzene ring is not limited to two and may be three or more.

The afore-mentioned glycerol diethers are as such known and are obtainedby known methods. Thus, for example, they are obtained in good yields byreacting a suitable phenol with epichlorohydrin in an alkaline medium.Suitable phenols are inter alia phenol itself, ortho-cresol,para-cresol, ortho-ethyl phenol, the different xylenols, ortho-chlrophenol, ortho-isopropylphenol, 2,6- diisopropyl-phenol, ortho-tertiarybutylphenol, 4-chloro- 2-isopropyl-S-methyl-benzene, para-tertiaryoctylphenol and the like. p

The proportion of carrier to be used may vary within wide limits andranges from 0.1 to parts per 1000 parts of the dyeing-preparation. Theamount of carrier must be adapted to the individual method ofapplication "used, that is to slayit will vary for printing and fordyeing.

printing, which requires an intermediatedrying of' the printed fabric.After the intermediate drying the fabric is subjected to heatrs'etting,which may be carried out in dry or moist conditions. The dry settingoperation is a heat treatment with hot air at "a temperature within therange from to 200 C., preferably from to C., for /2 to 5 minutes. Thewet treatment consists in steaming at 100 to 1 40" C., preferably at 110to 120 C., for 15 to 50 minutes and is carried out in any one of theapparatus conventionally used for steaming at these temperatures.

Apart from the carrier and the thickener the printing paste may containthe usual additives,such as antifoaming agents, for example fats, oils,mineral oils, oil of turpentine, silicones or water-insoluble metalsoaps. Hydrotropic agents, above all urea or thiourea, may likewise beadded. To protect the dyestuffs from possible reductive damage, forexample by the action of the fibre, it has been found advantageous toadd a mild oxidant, for example sodium meta-nitrobenzenesulphonate. Inthis connection it should also be mentioned that the dyeing preparationmay contain either one or several carriers. Thus, in addition to one orseveral compounds required according to this invention the preparationmay contain known carriers. As such carriers thereare often usedderivatives of benzene or of phenol, for example phenol, orthoorparaphenylphenol, chlorinated benzenes, xylenes, benzyl alcohol,aromatic estersor ethers, or benzoic or salicylic acid. It is onlynecessarysfor at least one of the carriers used to satisfy therequirements of this invention, while the others may be freely selected.

The advantages of the present process are above all the increasedyestuif exhaustion which, under optimum heat setting conditions,superior to that with the known processes and at lower-temperatures isstill acceptable,

Parts and percentages in the following examples are by weight.

Example 1 A fabric from triacetate fibres is printed with a printingpaste prepared from: 30 parts of a mixture of the dyestuffs of theformulae HO O OH O I II II I and at. 1'. I W Hi I. 4.110

500 parts of an aqueous thickening of 15% strength from commercial,modified locust bean flour, 30 parts of the compound of the formula OH ICH3 H30 and 440 parts of water.

The printed fabric is dried at about 80 C. and then steamed for 15minutes in a pressure steamer under a pressure of 1.75 atmospheres(gauge) at 110 C. The fabric is then finished off by rinsing in coldwater, washing in a bath heated at 50 C. which contain per 1000 parts ofwater 2 parts of any desired, mild synthetic detergent and 1 part ofsodium carbonate, and another cold rinse. The blue print is distinctlystronger than when a printing paste is used that does not contain theglycerol di-ortho-tolyl ether.

Example 2 A fabric from triacetate fibres is printed with a printingpaste prepared from: 30 parts of the dyestufi of the formula H? fl) I|IHCHz-CH2-OH I II HO O NH-CHz-OH2OH 420 parts of water parts of sodiummeta-nitrobenzenesulphonate 500 parts of an aqueous thickening ofstrength from commercial, modified locust bean flour 10 parts of anemulsion from:

60% pine oil 30% oleic acid 6.6% potassium hydroxide 3.4% water 30 partsof the compound of the formula I OH I CH 113C Example 3 A fabric fromtriacetate fibres is printed with a printing paste prepared from: 25parts of the dyestuff of the formula CH2CHz-O CH;

OH I a H30 The printed fabric is dried at about C. and then steamed for15 minutes at C. in a conventional steamer, and finished off asdescribed in Example 1. The resulting strong red-violet print displays ahigher degree of dyestutf fixation than when the carrier is omitted.

Similar results are obtained when the steaming process is replaced by atreatment with hot air at C. for 5 minutes or at 200 C. for one minute.

Example 4 A fabric from polyethyleneglycol terephthalate is printed witha printing paste prepared from: 30 parts of the dyestuff of the formulafl) NH;

OCH3

420 parts of water 10 parts of sodium meta-nitrobenzenesulfonate 500parts of an aqueous thickening of 15 strength from commercial, modifiedlocust bean flour 10 parts of an emulsion from:

60% pine oil 30% oleic acid 6.6% potassium hydroxide 3.4% Water, 30parts of the compound of the formula The printed fabric is dried atabout 80 C. and then subjected to a dry heat treatment for 1 minute at180 C., and the print is finished off as described in Example 1. Theresulting pink print displays a satisfactory degree of dyestutffixation, whereas it is unsatisfactory if the carrier is omitted.

What is claimed is:

1. Process for coloring textile materials from fibers selected from thegroup consisting of polyester and triacetate fibers with at the mostsparingly Water-soluble dyestuffs, which process comprises usingcoloring preparations containing at least one carrier of the formulaR-O-CH2-OH-CHz-O-Ri wherein R and R stand for radicals selected from thegroup consisting of identical and different aryl radicals.

2. 'Process for coloring textile materials according to claim 1, whichcomprises using coloring preparations containing at least one carrier ofthe formula A1 OH B wherein A, A '13 and B are selected from the groupconsisting of identical and different radicals selected from the groupconsisting of hydrogen, halogen and alkyl.

3. Process for coloring textile materials according to claim 1, whichcomprises using coloring preparations containing at least one carrier ofthe formula OH I A lkyl Alkyl wherein the alkyl radical contains 1 to 8carbon atoms.

4. Process for coloring textile materials according to claim 1, whichcomprises using coloring preparations containing at least one carrier ofthe formula (CH2) D1 H CH2) 11-1-11 1 (SE CH; H3 0 wherein n representsa whole number of at the most 2.

5. Process for coloring textile materials according to claim 1, whichcomprises using coloring preparations containing the carrier of theformula OH CH HaC 6. Process for coloring continuously textile materialsfrom triacetate fibers according to claim 1, which process comprisesusing coloring preparations containing as carrier glycerol diether fromepichlorohydrin and a commercial mixture of xylenols.

References Cited UNITED STATES PATENTS DONALD LEVY, Primary Examiner.

1. PROCESS FOR COLORING TEXTILE MATERIALS FROM FIBERS SELECTED FROM THEGROUP CONSISTING OF POLYESTER AND TRIACETATE FIBERS WITH AT THE MOSTSPARINGLY WATER-SOLUBLE DYESTUFFS, WHICH PROCESS COMPRISES USINGCOLORING PREPARATIONS CONTAINING AT LEAST ONE CARRIER OF THE FORMULA